CN1194992C - Method for removing residual rhodium catalyst from hydrogenated nitrile rubber - Google Patents
Method for removing residual rhodium catalyst from hydrogenated nitrile rubber Download PDFInfo
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- CN1194992C CN1194992C CNB021043949A CN02104394A CN1194992C CN 1194992 C CN1194992 C CN 1194992C CN B021043949 A CNB021043949 A CN B021043949A CN 02104394 A CN02104394 A CN 02104394A CN 1194992 C CN1194992 C CN 1194992C
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- hydrogenated nitrile
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Abstract
The present invention provides technology for removing a rhodium catalyst from a hydrogenated nitrile rubber solution. The hydrogenated nitrile rubber solution is processed by macroporous resin provided with a special functional group to remove the residual catalyst. The functional group is two or more than two functional groups in a sulfhydryl group, thiourea and isothiourea. The present invention is particularly suitable for the continuous processing of the rubber solution by an industrial device, such as an exchange column. The present invention has the characteristics of simple processing procedure, a few chelating resin dosage and high rhodium catalyst removing rate.
Description
Technical field
The invention provides a kind of technology that from the hydrogenated nitrile-butadiene rubber glue, removes residual rhodium catalyst.
Technical background
Hydrogenated nitrile-butadiene rubber (HNBR) is meant paracril (NBR) by hydrogenation, and the carbon-carbon double bond that has 80% (best 90～99.5%) at least is by hydrogenation.Unsaturated paracril be the monomer of the band itrile group (C ≡ N) that contains 3～5 α, β unsaturated carbon with the multipolymer that contains the conjugated diene monomer of 4～6 carbon, exemplary is an acrylonitrile butadiene copolymer.Unsaturated paracril obtains by free-radical emulsion polymerization.Exemplary is that acrylonitrile and butadiene obtains by free-radical emulsion polymerization, and wherein divinyl and vinyl cyanide binding capacity are 80～85: 20～50.
Hydrogenated nitrile-butadiene rubber is suitable to be that catalyzer carries out shortening to paracril and prepares with rhodium complex, because most of base metals are (as nickel naphthenate, alkyl cobalt, aluminum alkyls) not high and do not have selectivity to the hydrogenation efficiency of NBR, (C ≡ N) also reduces to itrile group.The utilization using rhodium complex catalysts prepares hydrogenated nitrile-butadiene rubber at United States Patent (USP) 4,464,515 and English Patent 1,558,499 in existing the disclosure.English Patent 1,558 is mentioned the (PPh with RhCl in 491
3)
3Make unsaturated paracril and select the catalyzer of hydrogenation.United States Patent (USP) 4,464 is mentioned the (PPh with RhH in 515
3)
4Make unsaturated paracril and select the catalyzer of hydrogenation.The technological process that these two pieces of patents are mentioned is roughly: unsaturated paracril is dissolved in the The suitable solvent, and then hydrogenation catalyst is dissolved in glue, feeds hydrogen and carries out hydrogenation.This hydrogenation technique is called homogeneous hydrogenation, reason be rubber with catalyzer exist same mutually in.
For above-mentioned any homogeneous hydrogenation technology, its advantage is to make the carbon-carbon double bond hydrogenation with very a spot of catalyzer.But homogeneous hydrogenation also has its weakness, exactly for heterogeneous hydrogenation, after reaction finished, removing catalyzer from system generally was the comparison difficulty, but not catalyzer needn't be dissolved in the solvent in the homogeneous hydrogenation, can remove catalyzer rapidly by filtration and sedimentary method.Because rhodium remains in the product, can have a strong impact on the aging resistance of hydrogenated nitrile-butadiene rubber, residual rhodium catalyst in the hydrogenated nitrile-butadiene rubber must be removed.Rhodium is again a kind of noble metal simultaneously, and reclaiming rhodium is that economic worth is arranged very much.United States Patent (USP) 4,396,761; Removing of hydrogenation of polymer of mentioning in 4,510,293 and 4,595,749 and hydrogenation catalyst all is extremely important technical process.A certain amount of using rhodium complex catalysts is more suitable for the selection hydrogenation of paracril, and promptly the selected hydrogenation of the carbon-carbon double bond in the paracril and hydrocarbon triple bond be not by hydrogenation.
United States Patent (USP) 4,944 is mentioned in 926 and is a kind ofly removed rhodium catalyst in the hydrogenated nitrile-butadiene rubber by the method for adding organic additive, if but these additives not exclusively from hydrogenated nitrile-butadiene rubber, separate, can cause secondary pollution to hydrogenated nitrile-butadiene rubber.United States Patent (USP) 4,985, disclose the resin that a kind of usefulness has single functional group such as sulfydryl, thiocarbamide, primary amine, secondary amine in 540 and removed rhodium catalyst in the hydrogenated nitrile-butadiene rubber, but consumption very big (portions of resin glue (butt) is 1: 3) when its resin is used for handling glue is continuously handled cycle time long (54 hours).
Summary of the invention
The object of the present invention is to provide a kind for the treatment of processes simple, the resin consumption is few, the method that the rhodium catalyst decreasing ratio is high.
Its method is: with the hydrogenated nitrile-butadiene rubber glue with have sulfydryl, thiocarbamide, isothiourea in the macroporous type resin of two or more functional groups fully contact, under 40～140 ℃ temperature, can remove the rhodium catalyst among the HNBR.
Here the macroporous type resin of indication just is meant the porous resin, and its pore volume is not less than 0.7ml/g, specific surface＞100m
2/ g wherein relatively is typically styrene diethylene benzene copoly mer.Other physical index is preferably: porosity (measuring with the mercury porosimeter):＞45%; Mean pore size:＞100 ; Size distribution: 0.2～2.5mm (butt); Tap density: 600～900g/l (wet basis).
The macroporous type resin is carried out functionalized processing, make it to have certain specific functional group, be proven technique already, and formed commodity.
When mean pore size less than 50 , when promptly using the microporous type resin, because little, the polymer in aperture can not enter inside, hole, make chain carrier reduce, and remove the weak effect of rhodium catalyst.
The typical implementation method of the present invention is that the resin that will have suitable functional group is contained in (as being a kind of cylindrical vessel that is used to adorn resin) in the packed tower.Between the median size 0.2～2.5mm of resin, tap density (wet basis) 600～900g/l is best, when the HNBR of rhodium-containing glue when the cylindrical container, the screen cloth that resin is had a pore is stayed in the container and is not pulled away.
The concentration range of glue is at 2～20% (weight meters), and preferably the rhodium-containing HNBR glue of 3～9% (weight meters) can remove the rhodium catalyst among the HNBR by resin column under 40～140 ℃ temperature.When temperature is lower than 40 ℃, certain removal effect is arranged, but efficient is very low, when temperature is higher than 160 ℃, should not use, because the part resin may be decomposed.Therefore, Zui You service temperature is: 60～120 ℃.
In the actual operational process of craft, pressure produces when falling and flowing through resin layer by the liquid small-particle, and when solution toughness and particle were very tiny, this phenomenon was greatly obvious.In optimization of the present invention was implemented, it was that the HNBR glue of rhodium-containing catalyst produces during by resin tower that pressure falls, and pressure is reduced to 0.7～20atm.
Because the resin that adopts among the present invention is the macroporous type resin that has two or more functional group in sulfydryl, thiocarbamide, the isothiourea, its synergy makes to be compared with the macroporous type resin that single use has a kind of functional group, reduce the resin consumption, reduced the processing cycle, improved the desorption efficient of unit time.Adopt method of the present invention, portions of resin glue (butt) is 1: 5 when being used for handling glue continuously, handling cycle time is 20 hours～30 hours, generally in the concentration range of 2～20% (weight meter) glue, can make that remaining rhodium is reduced to 8PPm among the HNBR of rhodium-containing 150PPm, therefore be specially adapted to the continuous processing of full scale plant glue.
Embodiment
Embodiment 1
The macroporous type resin is the multipolymer of benzene diene-Vinylstyrene, specific surface area 500m
2/ g, pore volume are 0.75ml/g, mean pore size: 200 ; Size distribution: 1～1.5mm (butt); Tap density: 880g/l (wet basis), and have thioureido, the functional group of isothioureido.
With the above-mentioned thioureido that has, the macroporous type resin of isothioureido functional group removes the using rhodium complex catalysts among the HNBR, and concrete technology is as follows:
Chlorobenzene solution to 6～25% paracril under the situation that rhodium catalyst and triphenylphosphine promotor exist carries out hydrogenation, can obtain HNBR.
To have thioureido, the about 10g of macroporous type resin of isothioureido functional group is arranged in and is about 20cm, in the ion exchange column of the about 1.0cm of inside diameter.Ion exchange column is 60～90 ℃ of following preheatings, and the HNBR glue of 1000g6% by ion exchange column, carries out removing of residual rhodium catalyst among the HNBR with the flow velocity of 0.5～2g/min under nitrogen protection.Glue after handling is taken out a little, and 60～70 ℃ of following vacuum-dryings, this glue sample is analyzed rhodium content with atomic emission spectrometry, and its result is 18ppm.
Undressed 6%HNBR glue takes out a little, and 60～70 ℃ of following vacuum-dryings, analyzing rhodium content with atomic emission spectrometry is 154ppm, so the decreasing ratio of rhodium is 88.2%.
Embodiment 2
Still have sulfydryl with about 10g with the macroporous type resin of embodiment 1 identical benzene diene-divinyl benzene copolymer, isothioureido functional group, remove residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, rhodium content is 20ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 87%.
Embodiment 3
Still have sulfydryl with about 10g with the macroporous type resin of embodiment 1 identical benzene diene-divinyl benzene copolymer, thioureido, isothiourea mixes functional group's (sulfydryl: thioureido: isothiourea=90-98: 2-8: 0-3)., removing residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, and rhodium content is 8ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 94.8%.
Embodiment 4
Still have sulfydryl, thioureido mixing functional group (sulfydryl: thioureido=90-98: 2-10) with about 10g with the macroporous type resin of embodiment 1 identical benzene diene-divinyl benzene copolymer, remove residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, rhodium content is 16ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 89.6%.
Comparative Examples 1
Still only have sulfydryl with about 10g with the macroporous type resin of embodiment 1 identical benzene diene-divinyl benzene copolymer, remove residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, and rhodium content is 60ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 61%.
Comparative Examples 2
Still only have isothiourea functional group with about 10g with the macroporous type resin of embodiment 1 identical benzene diene-divinyl benzene copolymer, remove residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, rhodium content is 39ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 74.7%.
Comparative Examples 3
With the microporous type resin of about 10g benzene diene-divinyl benzene copolymer, specific surface area 10m
2/ g, pore volume are 0.2ml/g, mean pore size: 40 ; Be to have sulfydryl, thioureido mixing functional group, remove residual rhodium catalyst in the HNBR glue with it, technological process is described with embodiment 1, and rhodium content is 117ppm among the HNBR after the processing, and the decreasing ratio of rhodium is 24%.
Claims (3)
1. the removal methods of a hydrogenated nitrile-butadiene rubber residual rhodium catalyst, the hydrogenated nitrile-butadiene rubber glue fed in the resin have functional group rhodium catalyst is removed, it is characterized in that with the hydrogenated nitrile-butadiene rubber glue with have sulfydryl, thiocarbamide, isothiourea in the macroporous type resin of two or more functional group fully contact, under 40～140 ℃ temperature, can remove the rhodium catalyst in the hydrogenated nitrile-butadiene rubber.
2. method according to claim 1 is characterized in that the pore volume of macroporous type resin is not less than 0.7ml/g, specific surface＞100m
2/ g.
3. method according to claim 1 and 2 is characterized in that the macroporous type resin is vinylbenzene-divinyl benzene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021043949A CN1194992C (en) | 2002-03-07 | 2002-03-07 | Method for removing residual rhodium catalyst from hydrogenated nitrile rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021043949A CN1194992C (en) | 2002-03-07 | 2002-03-07 | Method for removing residual rhodium catalyst from hydrogenated nitrile rubber |
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| Publication Number | Publication Date |
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| CN1443784A CN1443784A (en) | 2003-09-24 |
| CN1194992C true CN1194992C (en) | 2005-03-30 |
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| CNB021043949A Expired - Fee Related CN1194992C (en) | 2002-03-07 | 2002-03-07 | Method for removing residual rhodium catalyst from hydrogenated nitrile rubber |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924726B (en) * | 2012-11-13 | 2015-05-20 | 北京化工大学 | Method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation |
| TWI653246B (en) * | 2013-12-30 | 2019-03-11 | 艾朗希歐德意志有限公司 | Hydrogenated nitrile rubber containing phosphine oxide or diphosphine oxide (2) |
| TWI667069B (en) * | 2013-12-30 | 2019-08-01 | 德商艾朗希歐德意志有限公司 | Hydrogenated nitrile rubber containing phosphine sulphide or diphosphine sulphide |
| TWI653297B (en) * | 2013-12-30 | 2019-03-11 | 艾朗希歐德意志有限公司 | Hydrogenated nitrile rubber containing phosphine oxide or diphosphine oxide (1) |
| CN105985456B (en) * | 2015-02-05 | 2017-11-07 | 中国石油天然气股份有限公司 | A kind of method of metal rhodium in removal hydrogenated nitrile-butadiene rubber |
| CN107722145B (en) * | 2016-08-10 | 2020-07-24 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
| CN107722147B (en) * | 2016-08-10 | 2020-06-09 | 中国石油化工股份有限公司 | Selective hydrogenation method of polar polymer |
| CN108329489B (en) * | 2017-01-19 | 2021-08-03 | 中国石油化工股份有限公司 | Chelate resin and pretreatment method, noble metal removing method and method for removing noble metal catalyst from unsaturated copolymer hydrogenation liquid |
| CN108329408B (en) * | 2017-01-19 | 2021-02-05 | 中国石油化工股份有限公司 | Method for removing rhodium metal organic catalyst from hydrogenated nitrile butadiene rubber solution |
| CN108329488B (en) * | 2017-01-19 | 2021-04-09 | 中国石油化工股份有限公司 | Chelate resin and pretreatment method, noble metal removing method and method for removing noble metal catalyst from unsaturated copolymer hydrogenation liquid |
| CN109266443A (en) * | 2018-11-06 | 2019-01-25 | 武汉九珑人福药业有限责任公司 | The preparation method of pharmaceutical grade rilanit special |
| CN114426588A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Method for removing noble metal catalyst from unsaturated copolymer hydrogenation solution |
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